US6437178B2 - O-aminophenolcarboxylic acid and o-aminothiophenolcarboxylic acid - Google Patents
O-aminophenolcarboxylic acid and o-aminothiophenolcarboxylic acid Download PDFInfo
- Publication number
- US6437178B2 US6437178B2 US09/901,218 US90121801A US6437178B2 US 6437178 B2 US6437178 B2 US 6437178B2 US 90121801 A US90121801 A US 90121801A US 6437178 B2 US6437178 B2 US 6437178B2
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- US
- United States
- Prior art keywords
- acid
- group
- aminophenolcarboxylic
- benzyl
- carbon atoms
- Prior art date
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- Expired - Lifetime
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- 0 Cc1*:*:*:*c1*c1*:*:*:*c1C.Cc1*:*:*:*c1C.Cc1*:*:*c(*c2*:*:*:*:*2)c1C.Cc1*:*:*c(*c2*:*:*:*c2C)*1.Cc1*:*:*c(*c2*:*:*c(C)*2)*1.Cc1*:*:*c(C)*1.Cc1*:*:*c2*:*:*cc12.Cc1*:*:*c2c(C)*:*:*c12.Cc1*:*c(*c2*:*:*:*:*2)c(C)*1.Cc1*:*c(*c2*:*:*:*c2C)*:*1.Cc1*:*c(*c2*:*:*c(C)*2)*:*1.Cc1*:*c(*c2*:*c(C)*:*2)*:*1.Cc1*:*c(C)*:*1.Cc1*:*c(C)c(*c2*:*:*:*:*2)*1.Cc1*:*c(C)c2*:*:*:*c12.Cc1*:*c2*:*:*:*c2c1.Cc1*:*c2*:*:*c(C)c2*1.Cc1*:*c2*:*c(C)*c2*1.Cc1*:*c2*c(C)*:*c2*1.Cc1*:*c2c(C)*:*:*c2*1.Cc1*c(C)*c(*c2*:*:*:*:*2)*1.Cc1*c2*:*:*:*c2*c1C.Cc1*cc2*:*:*:*c2*1 Chemical compound Cc1*:*:*:*c1*c1*:*:*:*c1C.Cc1*:*:*:*c1C.Cc1*:*:*c(*c2*:*:*:*:*2)c1C.Cc1*:*:*c(*c2*:*:*:*c2C)*1.Cc1*:*:*c(*c2*:*:*c(C)*2)*1.Cc1*:*:*c(C)*1.Cc1*:*:*c2*:*:*cc12.Cc1*:*:*c2c(C)*:*:*c12.Cc1*:*c(*c2*:*:*:*:*2)c(C)*1.Cc1*:*c(*c2*:*:*:*c2C)*:*1.Cc1*:*c(*c2*:*:*c(C)*2)*:*1.Cc1*:*c(*c2*:*c(C)*:*2)*:*1.Cc1*:*c(C)*:*1.Cc1*:*c(C)c(*c2*:*:*:*:*2)*1.Cc1*:*c(C)c2*:*:*:*c12.Cc1*:*c2*:*:*:*c2c1.Cc1*:*c2*:*:*c(C)c2*1.Cc1*:*c2*:*c(C)*c2*1.Cc1*:*c2*c(C)*:*c2*1.Cc1*:*c2c(C)*:*:*c2*1.Cc1*c(C)*c(*c2*:*:*:*:*2)*1.Cc1*c2*:*:*:*c2*c1C.Cc1*cc2*:*:*:*c2*1 0.000 description 9
- HCLGNWGGMBEEHB-UHFFFAOYSA-N Nc1ccc(Oc2ccc(C(=O)O)cc2)cc1O Chemical compound Nc1ccc(Oc2ccc(C(=O)O)cc2)cc1O HCLGNWGGMBEEHB-UHFFFAOYSA-N 0.000 description 2
- JMPDZZNRRIUBQR-UHFFFAOYSA-N C.C.CC.CC.COCOC.OOCc1ccccc1.[H]c1ccccc1N Chemical compound C.C.CC.CC.COCOC.OOCc1ccccc1.[H]c1ccccc1N JMPDZZNRRIUBQR-UHFFFAOYSA-N 0.000 description 1
- USWOTTAGRTYUKD-RAQLBBNBSA-N C.C.CC.CC.C[3H]C[3H]C.O=C(O)c1ccccc1.[H]c1ccccc1N Chemical compound C.C.CC.CC.C[3H]C[3H]C.O=C(O)c1ccccc1.[H]c1ccccc1N USWOTTAGRTYUKD-RAQLBBNBSA-N 0.000 description 1
- ZLKXLJIODIKNFH-UHFFFAOYSA-N C.CC.Cc1ccccc1.[H]C Chemical compound C.CC.Cc1ccccc1.[H]C ZLKXLJIODIKNFH-UHFFFAOYSA-N 0.000 description 1
- CRDCTUKMWMHPQR-JNWMDIJTSA-N C.CC.[3H]C.[3H]c1ccccc1[N+](=O)[O-] Chemical compound C.CC.[3H]C.[3H]c1ccccc1[N+](=O)[O-] CRDCTUKMWMHPQR-JNWMDIJTSA-N 0.000 description 1
- MVRHWWOKGXIPOQ-UHFFFAOYSA-N C=C=Nc1ccc(Cc2ccc(C#COCc3ccccc3)cc2)cc1OCc1ccccc1 Chemical compound C=C=Nc1ccc(Cc2ccc(C#COCc3ccccc3)cc2)cc1OCc1ccccc1 MVRHWWOKGXIPOQ-UHFFFAOYSA-N 0.000 description 1
- HBGCWXDXQGFHPQ-UHFFFAOYSA-N C=C=Nc1ccc(Oc2c(F)c(F)c(-c3c(F)c(F)c(Oc4ccc(C(=O)OCc5ccccc5)cc4)c(F)c3F)c(F)c2F)cc1OCc1ccccc1 Chemical compound C=C=Nc1ccc(Oc2c(F)c(F)c(-c3c(F)c(F)c(Oc4ccc(C(=O)OCc5ccccc5)cc4)c(F)c3F)c(F)c2F)cc1OCc1ccccc1 HBGCWXDXQGFHPQ-UHFFFAOYSA-N 0.000 description 1
- JLLDHHQPWYXHRO-UHFFFAOYSA-N CCC.CCC.CCC.CCC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.F.F.F.c1ccc2ccccc2c1.c1ccc2ccccc2c1.c1ccc2ccccc2c1.c1ccc2ccccc2c1.c1ccccc1.c1ccccc1.c1ccccc1.c1ccccc1.c1ccccc1.c1ccccc1.c1ccccc1.c1ccccc1.c1ccccc1.c1ccccc1 Chemical compound CCC.CCC.CCC.CCC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.COC.F.F.F.c1ccc2ccccc2c1.c1ccc2ccccc2c1.c1ccc2ccccc2c1.c1ccc2ccccc2c1.c1ccccc1.c1ccccc1.c1ccccc1.c1ccccc1.c1ccccc1.c1ccccc1.c1ccccc1.c1ccccc1.c1ccccc1.c1ccccc1 JLLDHHQPWYXHRO-UHFFFAOYSA-N 0.000 description 1
- UKZPHQVWZHSCNP-UHFFFAOYSA-N COc1cc(Oc2ccc(C)cc2)ccc1N Chemical compound COc1cc(Oc2ccc(C)cc2)ccc1N UKZPHQVWZHSCNP-UHFFFAOYSA-N 0.000 description 1
- HKBDYXCFEVHPTI-UHFFFAOYSA-N Cc1cc(Oc2c(F)c(F)nc(Oc3ccc(C(=O)O)cc3)c2F)ccc1N Chemical compound Cc1cc(Oc2c(F)c(F)nc(Oc3ccc(C(=O)O)cc3)c2F)ccc1N HKBDYXCFEVHPTI-UHFFFAOYSA-N 0.000 description 1
- BSMKLKTXFZDTNS-UHFFFAOYSA-N Fc1c(F)c(F)c(C(F)(F)F)c(Oc2ccc(COOCc3ccccc3)cc2)c1F Chemical compound Fc1c(F)c(F)c(C(F)(F)F)c(Oc2ccc(COOCc3ccccc3)cc2)c1F BSMKLKTXFZDTNS-UHFFFAOYSA-N 0.000 description 1
- OXNRKOYKWKYYLQ-UHFFFAOYSA-N N=C1C=CC(Oc(cc2)ccc2C(O)=O)=CC1O Chemical compound N=C1C=CC(Oc(cc2)ccc2C(O)=O)=CC1O OXNRKOYKWKYYLQ-UHFFFAOYSA-N 0.000 description 1
- FWBRAFSACZYPEL-UHFFFAOYSA-N Nc1ccc(Oc2c(F)c(F)c(-c3c(F)c(F)c(Oc4ccc(C(=O)O)cc4)c(F)c3F)c(F)c2F)cc1O Chemical compound Nc1ccc(Oc2c(F)c(F)c(-c3c(F)c(F)c(Oc4ccc(C(=O)O)cc4)c(F)c3F)c(F)c2F)cc1O FWBRAFSACZYPEL-UHFFFAOYSA-N 0.000 description 1
- ATFHYBKJURKORG-UHFFFAOYSA-N Nc1ccc(Oc2c(F)c(F)c(C(F)(F)F)c(Oc3ccc(CC=O)cc3)c2F)cc1O Chemical compound Nc1ccc(Oc2c(F)c(F)c(C(F)(F)F)c(Oc3ccc(CC=O)cc3)c2F)cc1O ATFHYBKJURKORG-UHFFFAOYSA-N 0.000 description 1
- BCNIYAYTJBMUTQ-UHFFFAOYSA-N O=C(OCc1ccccc1)c1ccc(Oc2c(F)c(F)c(-c3c(F)c(F)c(F)c(F)c3F)c(F)c2F)cc1 Chemical compound O=C(OCc1ccccc1)c1ccc(Oc2c(F)c(F)c(-c3c(F)c(F)c(F)c(F)c3F)c(F)c2F)cc1 BCNIYAYTJBMUTQ-UHFFFAOYSA-N 0.000 description 1
- IBYLNGIFOKDSLH-UHFFFAOYSA-N O=C(OCc1ccccc1)c1ccc(Oc2ccc([N+](=O)[O-])c(OCc3ccccc3)c2)cc1 Chemical compound O=C(OCc1ccccc1)c1ccc(Oc2ccc([N+](=O)[O-])c(OCc3ccccc3)c2)cc1 IBYLNGIFOKDSLH-UHFFFAOYSA-N 0.000 description 1
- WISYZVIJTWACKH-UHFFFAOYSA-N O=C(OCc1ccccc1)c1ccc(Oc2nc(F)c(F)c(F)c2F)cc1 Chemical compound O=C(OCc1ccccc1)c1ccc(Oc2nc(F)c(F)c(F)c2F)cc1 WISYZVIJTWACKH-UHFFFAOYSA-N 0.000 description 1
- MTYILHJPOZEVKS-UHFFFAOYSA-N O=C(OCc1ccccc1)c1ccc(Oc2nc(F)c(F)c(Oc3ccc([N+](=O)[O-])c(OCc4ccccc4)c3)c2F)cc1 Chemical compound O=C(OCc1ccccc1)c1ccc(Oc2nc(F)c(F)c(Oc3ccc([N+](=O)[O-])c(OCc4ccccc4)c3)c2F)cc1 MTYILHJPOZEVKS-UHFFFAOYSA-N 0.000 description 1
- LRJSTEIBKUFQHP-UHFFFAOYSA-N O=[N+]([O-])c1ccc(Oc2c(F)c(F)c(C(F)(F)F)c(Oc3ccc(COOCc4ccccc4)cc3)c2F)cc1OCc1ccccc1 Chemical compound O=[N+]([O-])c1ccc(Oc2c(F)c(F)c(C(F)(F)F)c(Oc3ccc(COOCc4ccccc4)cc3)c2F)cc1OCc1ccccc1 LRJSTEIBKUFQHP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
- C07D213/643—2-Phenoxypyridines; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
- C07C217/90—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. amino-diphenylethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
- C07C69/92—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with etherified hydroxyl groups
Definitions
- the invention relates to novel o-aminophenolcarboxylic acids and o-aminothiophenolcarboxylic acids, which are also jointly abbreviated to o-amino(thio)phenolcarboxylic acids, and to a process for their preparation.
- o-Aminophenolcarboxylic acids are needed, in particular, for the preparation of high-temperature-stable polymers, such as polybenzoxazoles (PBOs) and their precursors.
- PBOs polybenzoxazoles
- the use of o-aminophenolcarboxylic acids has significant advantages. For example, an o-aminophenolcarboxylic acid can be reacted with itself, i.e. a second monomer is not absolutely necessary for the polymerization. This allows purity monitoring and storage to be simplified.
- the stoichiometry is predefined, i.e.
- PBO precursors in the form of a photosensitive composition can be structured inexpensively by direct methods, i.e. without an auxiliary resist.
- PBO precursors offer the advantage of positive structurability and aqueous-alkaline development (see EP 0 023 662 B1 and EP 0 264 678 B1).
- the PBO precursors used must be substantially transparent at the exposure wavelength and sufficiently soluble in the developer, which preferably contains no metal ions.
- polybenzoxazoles also have the manor advantage that they—compared with the cyclized final product—as readily soluble precursors, can be applied to a substrate and then cyclized, during which the solubility and thus the sensitivity to solvents and other process chemicals decreases greatly.
- o-Aminophenolcarboxylic acids are disclosed, for example, in GB 811,758 and GB 1,283,476.
- the water absorption in boiling water after 24 h is 0.77%.
- the object of the invention is to provide o-aminophenolcarboxylic acids and o-aminothiophenolcarboxylic acids which are suitable for the preparation of polymers which satisfy the greatly increased demands of microelectronics.
- the o-amino(thio)phenolcarboxylic acids should, in particular, enable the preparation of readily soluble polymer precursors which, after cyclization on a substrate, give polybenzoxazoles or polybenzothiazoles of low moisture absorption and high degree of planarization.
- a 1 to A 7 are independently of one another —H, CH 3 , OCH 3 , CH 2 CH 3 or OCH 2 CH 3 ;
- T is O or S,; m is 0 or 1;
- Z is one of the following carbocyclic or heterocyclic aromatic radicals:
- M a single bond, (CH 3 ) n , (CF 2 ) n , CH(CH 3 ), CH(CF 3 ), CF(CH 3 ), CF(CF 3 ), C(CH 3 ) 2 , C(CF 3 ) 2 , CH(CH 6 H 5 ), CH(C 6 F 5 ), CF(C 6 H 5 ), CF(C 6 F 5 ), C(CH 3 (C 6 H 6 ), C(CH 3 ) (C 6 F 5 ), C(CF 3 ) (C 6 H 5 ), C(CF 3 ) (C 6 F 5 ), C(C 6 H 5 ) 2 , C(C 6 F 6 ) 2 , CO, SO 2
- novel compounds have, for example, the following preferred structure:
- the ether bridges are apparently responsible for the good solubility and the good planarization properties of the polymer precursors prepared therewith.
- the characterization “A 1 -A 3 ” and “A 4 -A 7 ” in the structural formula means that the aminophenyl groups and carboxyphenyl groups contain radicals A 1 , A 2 and A 3 , and A 4 , A 5 , A 6 and A 7 respectively.
- o-amino(thio)phenolcarboxylic acids can be prepared by
- nitrophenol or nitrothiophenol of the structure
- R 1 alkyl (having 1 to 5 carbon atoms), phenyl or benzyl, A 1 to A 7 , T and Z are as defined above, and R is one of the following radicals: alkyl, alkoxyalkyl, alkenyl, alkoxyalkenyl, alkynyl or alkoxyalkynyl, each having a maximum of 6 carbon atoms, phenyl, phenacyl or benzyl, and benzylalkyl, benzylalkenyl, benzyloxyalkyl, benzyloxyalkenyl, benzylalkoxyalkyl or benzylalkoxyalken
- a halogen-containing ester or a corresponding nitrile is thus reacted with a nitro(thio)phenol having an R-protected hydroxyl or mercapto group in the opposition to the nitro group.
- the nitro compound formed is then reduced to the corresponding amino compound, the ester or nitrile group is hydrolyzed to the carboxyl group, and the protecting group R is removed
- o-amino(thio)phenolcarboxylic acids can also be prepared by
- X is a halogen atom
- E is CN or COOR 1
- R 1 alkyl (having 1 to 5 carbon atoms) , phenyl or benzyl, A 1 to A 7 , T and Z are as defined above, and R is one of the above mentioned radicals;
- a halogen-containing nitro compound having a protected hydroxyl or mercapto group in the o-position to the nitro group is thus reacted with a (thio)phenol containing an ester or nitrile group.
- the nitro compound formed is then—in the manner indicated above—subjected to a reduction, hydrolysis and removal of protecting group.
- the protecting group R is preferably an alkyl, alkoxyalkyl, phenyl or benzyl group. It is an important advantage that the radical RT is stable in the reaction between the halogen compound and the nitro(thio)phenol, but can subsequently be removed.
- the reaction between the halogen compound and the nitro(thio)phenol, in which an ether or thioether bridge is formed, is carried out in the presence of a base.
- This base is preferably a carbonate or hydrogencarbonate of an alkali metal or alkaline earth metal, such as sodium carbonate or potassium carbonate.
- Formation of the (thio ether requires at least a stoichiometric amount of the base. It may also be advantageous to use an organic base containing a tertiary N atom, for example triethylamine or pyridine.
- the nitro(thio)phenol can also be replaced by a corresponding alkali metal salt, for example the potassium salt.
- a base is not absolutely necessary for the reaction with the halogen compound.
- a reaction temperature in the range from ⁇ 10 to 80° C. has proven suitable. Temperatures ⁇ 80° C. are preferred owing to the greater selectivity of the reaction.
- Suitable solvents are, in particular, dimethylformamide, diethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, ⁇ -butyrolactone, acetonitrile, tetrahydrofuran and pyridine. In principle, however, all polar aprotic solvents in which the starting compounds are soluble can be used.
- the reduction of the nitro compound can be carried out, for example, by catalytic hydrogenation using, for example hydrogen on Pd/C catalyst. In principle, however, all the processes which are suitable for reducing the nitro group to the amino group are suitable.
- the hydrolysis of the ester or nitrile group can be carried out, for example, using potassium hydroxide.
- the protecting group can be removed using, for example, trifluoroacetic acid or titanium tetrachloride. These reactions can be carried out in separate process steps; the sequence of the process steps is unimportant.
- the polymer precursors prepared from the o-amino(thio)phenolcarboxylic acids of the invention and having improved properties compared with the prior art are soluble in many organic solvents, such as acetone, cyclohexanone, N-methylpyrrolidone, diethylene glycol mono- or diethyl ether, ethyl lactate and ⁇ -butyrolactone, and in aqueous-alkaline developers containing no metal ions. They are therefore highly suitable as base polymers for dielectrics which can be photostructured positively and can be developed in aqueous-alkaline media.
- the precursors can easily be applied to substrates, such as silicone wafers, by spin-coating methods, they form uniform films, and can readily be cyclized on the substrate.
- substrates such as silicone wafers
- a particular advantage of the precursors prepared from these o-amino(thio)phenolcarboxylic acids is their high planarization capacity and low moisture absorption.
- the yellow-beige solution is evaporated to half in a rotary evaporator and left to stand overnight at room temperature, during which the reaction product precipitates out in crystalline form.
- the reaction product is then separated off and dried for 48 hours under nitrogen at 40° C./10 mbar in a vacuum drying cabinet (yield: 91%).
- the organic phase is then washed three times with water, dried over sodium sulfate and evaporated in a rotary evaporator until the reaction product precipitates out.
- the reaction product is stirred in petroleum ether (boiling range 40 to 60° C. for 2 hours, filtered off via a Buchner funnel and then dried for 48 hours under nitrogen at 40° C./10 mbar in a vacuum drying cabinet (yield: 91%).
- the crude product is washed by shaking with 300 ml of ethyl acetate and 700 ml of water, and the organic phase is washed three times with water and evaporated in a rotary evaporator until the reaction product precipitates out.
- the reaction product is then recrystallized from a mixture of ethyl acetate and n-hexane (volume ratio 1:1) and then dried for 48 hours under nitrogen at 40° C./10 mbar in a vacuum drying cabinet (yield: 92%).
- the clear solution obtained is evaporated in a rotary evaporator until the reaction product precipitates out.
- the reaction product is then stirred in n-hexane, filtered off through a fluted filter and then dried for 48 hours under nitrogen at 40° C./10 mbar in a vacuum drying cabinet (yield: 95%).
- the crude product is washed by shaking with 300 ml of ethyl acetate and 700 ml of water, and the organic phase is washed three times with water and evaporated in a rotary evaporator until the react on product precipitates out.
- the reaction product is then recrystallized from a mixture of ethyl acetate and n-hexane (volume ratio 1:1) and then dried for 48 hours under nitrogen at 40° C./10 mbar in a vacuum drying cabinet (yield: 94%).
- the orange solution is evaporated to half in a rotary evaporator and left to stand overnight at room temperature, during which the reaction product precipitates out in crystalline form.
- the reaction product is then dried for 48 hours under nitrogen at 40° C./10 mbar in a vacuum drying cabinet (yield: 95%).
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
Abstract
Description
Claims (13)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/901,218 US6437178B2 (en) | 1997-09-24 | 2001-07-09 | O-aminophenolcarboxylic acid and o-aminothiophenolcarboxylic acid |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19742194 | 1997-09-24 | ||
DE19742194 | 1997-09-24 | ||
DE19742194.6 | 1997-09-24 | ||
US09/161,147 US6310238B1 (en) | 1997-09-24 | 1998-09-24 | O-amino(thio)phenolcarboxylic acids, and their preparation |
US09/901,218 US6437178B2 (en) | 1997-09-24 | 2001-07-09 | O-aminophenolcarboxylic acid and o-aminothiophenolcarboxylic acid |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/161,147 Division US6310238B1 (en) | 1997-09-24 | 1998-09-24 | O-amino(thio)phenolcarboxylic acids, and their preparation |
Publications (2)
Publication Number | Publication Date |
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US20010056203A1 US20010056203A1 (en) | 2001-12-27 |
US6437178B2 true US6437178B2 (en) | 2002-08-20 |
Family
ID=7843502
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/161,147 Expired - Lifetime US6310238B1 (en) | 1997-09-24 | 1998-09-24 | O-amino(thio)phenolcarboxylic acids, and their preparation |
US09/901,218 Expired - Lifetime US6437178B2 (en) | 1997-09-24 | 2001-07-09 | O-aminophenolcarboxylic acid and o-aminothiophenolcarboxylic acid |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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US09/161,147 Expired - Lifetime US6310238B1 (en) | 1997-09-24 | 1998-09-24 | O-amino(thio)phenolcarboxylic acids, and their preparation |
Country Status (4)
Country | Link |
---|---|
US (2) | US6310238B1 (en) |
EP (1) | EP0905123B1 (en) |
JP (1) | JP3681554B2 (en) |
DE (1) | DE59802413D1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030087190A1 (en) * | 2001-09-14 | 2003-05-08 | Recai Sezi | Photosensitive formulation for buffer coatings, film including the formulation, and method for manufacturing electronics using the formulation |
US20030099904A1 (en) * | 2001-09-14 | 2003-05-29 | Recai Sezi | Photosensitive formulation for buffer coatings, film containing the photosensitive formulation, and method for fabricating electronics with the photosensitive formulation |
US20030134226A1 (en) * | 2001-09-14 | 2003-07-17 | Recai Sezi | Polybenzoxazoles from poly-o-hydroxyamide, novel poly-o-hydroxyamides, preparation processes therefor, and their application in microelectronics |
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DE10011608A1 (en) * | 2000-03-10 | 2001-10-18 | Infineon Technologies Ag | Bis-o-aminophenols and o-aminophenol carboxylic acids |
US20050025993A1 (en) * | 2003-07-25 | 2005-02-03 | Thompson Mark E. | Materials and structures for enhancing the performance of organic light emitting devices |
DE602004028150D1 (en) * | 2003-11-26 | 2010-08-26 | Pfizer Prod Inc | AMINOPYRAZOL DERIVATIVES AS GSK-3 INHIBITORS |
ES2610588T3 (en) | 2008-05-27 | 2017-04-28 | Dako Denmark A/S | Compositions and methods for the detection of chromosomal aberrations with novel hybridization buffers |
WO2010097655A1 (en) | 2009-02-26 | 2010-09-02 | Dako Denmark A/S | Compositions and methods for rna hybridization applications |
EP2761028A1 (en) | 2011-09-30 | 2014-08-06 | Dako Denmark A/S | Hybridization compositions and methods using formamide |
EP2768974B1 (en) | 2011-10-21 | 2017-07-19 | Dako Denmark A/S | Hybridization compositions and methods |
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- 1998-09-12 DE DE59802413T patent/DE59802413D1/en not_active Expired - Lifetime
- 1998-09-24 JP JP27039198A patent/JP3681554B2/en not_active Expired - Fee Related
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GB811758A (en) | 1955-10-28 | 1959-04-08 | Du Pont | Polybenzoxazoles and method of preparing the same |
GB1283476A (en) | 1970-03-05 | 1972-07-26 | Holliday Co Ltd L B | Dyeing of synthetic fibres |
US4248962A (en) * | 1977-12-23 | 1981-02-03 | Eastman Kodak Company | Photographic emulsions, elements and processes utilizing release compounds |
EP0023662A1 (en) | 1979-08-01 | 1981-02-11 | Siemens Aktiengesellschaft | Heat-resistent positive photoresists and process for the preparation of heat-resistent relief structures |
US4526861A (en) * | 1983-03-29 | 1985-07-02 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material comprising coupler having nitrogen-containing heterocyclic ring |
US4743595A (en) * | 1984-06-14 | 1988-05-10 | Fuji Photo Film Co., Ltd. | Process for preparing 2-amino-5-nitrophenol derivatives |
EP0264678A1 (en) | 1986-10-02 | 1988-04-27 | Hoechst Celanese Corporation | Polyamides with hexafluoroisopropylidene groups, positively acting photosensitive compositions, and recording materials using them |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030087190A1 (en) * | 2001-09-14 | 2003-05-08 | Recai Sezi | Photosensitive formulation for buffer coatings, film including the formulation, and method for manufacturing electronics using the formulation |
US20030099904A1 (en) * | 2001-09-14 | 2003-05-29 | Recai Sezi | Photosensitive formulation for buffer coatings, film containing the photosensitive formulation, and method for fabricating electronics with the photosensitive formulation |
US20030134226A1 (en) * | 2001-09-14 | 2003-07-17 | Recai Sezi | Polybenzoxazoles from poly-o-hydroxyamide, novel poly-o-hydroxyamides, preparation processes therefor, and their application in microelectronics |
US6884567B2 (en) * | 2001-09-14 | 2005-04-26 | Infineon Technologies Ag | Photosensitive formulation for buffer coatings, film containing the photosensitive formulation, and method for fabricating electronics with the photosensitive formulation |
US7070904B2 (en) * | 2001-09-14 | 2006-07-04 | Infineon Technologies Ag | Polybenzoxazoles from poly-o-hydroxyamide, novel poly-o-hydroxyamides, preparation processes therefor, and their application in microelectronics |
Also Published As
Publication number | Publication date |
---|---|
JP3681554B2 (en) | 2005-08-10 |
EP0905123B1 (en) | 2001-12-12 |
US20010056203A1 (en) | 2001-12-27 |
JPH11158128A (en) | 1999-06-15 |
US6310238B1 (en) | 2001-10-30 |
EP0905123A1 (en) | 1999-03-31 |
DE59802413D1 (en) | 2002-01-24 |
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